Compositions and methods for selective deposition modeling

ABSTRACT

Phase change compositions that are solid at ambient temperature and liquid at an elevated temperature above ambient temperature are disclosed for advantageous use in selective deposition modeling methods for building three-dimensional objects. A phase change composition according to the disclosed invention is a semi-crystalline component mixture having a freezing point of at least about 68° C., a melting point of at least about 88° C. and a viscosity of about 13 centipoise at 135° C. The composition includes a plurality of waxes having a broad melting point range and molecular weight range. Three-dimensional objects having minimal curl, delamination and stress cracks can be produced at a faster rate than heretofore known by using selective deposition modeling techniques employing the disclosed compositions.

“This is a divisional of U.S. patent application No. 09/258,048 filedFeb. 25, 1999, now pending.”

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions and methods for buildingthree-dimensional objects and, more particularly, to phase changecompositions and selective deposition modeling methods for buildingthree-dimensional objects utilizing such compositions.

2. Description of the Related Art

The art of building three-dimensional objects using selective depositionmodeling methods is a rapidly-developing technology. In once knownselective deposition modeling method, a phase change composition, i.e.,a composition that is a solid at ambient temperature and a liquid at anelevated temperature above ambient temperature, is melted by heating anddeposited in liquid form onto a build platform in a controlledenvironment to form a multi-layered three-dimensional object on alayer-by-layer basis. The composition is deposited onto the buildplatform using a modified ink jet print head having a multiplicity ofnozzles, e.g., 352 nozzles. A computer program prescribes theconfiguration of each layer of the object and controls the nozzles fromwhich material is deposited during the deposition of any given layer tomeet that layer's configuration. The material of each layer at leastpartially solidifies as a successive layer of material is selectivelydeposited thereupon from the print head. In this manner, the object isformed layer-by-layer into a final object having a desired shape andcross-section.

3D Systems, Inc., the Assignee of the present invention, has previouslydeveloped apparatus, methods and compositions for the selectivedeposition modeling of three-dimensional objects as described above.Thus, PCT Patent Application No. WO 97-11835 to Earl et al., publishedApr. 3, 1997, describes a rapid prototyping apparatus and method forbuilding three-dimensional objects employing selective depositionmodeling. PCT Patent Application No. WO 97-11837 to Ley-den et al.,published Apr. 3, 1997, describes computer methods and apparatus formanipulating object and object support data and controlling object buildstyles for use in building three-dimensional objects by selectivedeposition modeling. U.S. Pat. No. 5,855,836 to Leyden, et al. issuedJan. 5, 1999, discloses phase change compositions for use in buildingthree-dimensional objects by selective deposition modeling techniques.The contents of each of the above-noted published applications areexpressly incorporated herein by reference.

Phase change compositions possessing specific physical properties aredesirable in order to avoid various problems that can arise during andafter creation of an object by selective deposition modeling techniques.The currently existing problems in building three-dimensional objectsusing selective deposition modeling are many. Such problems includecurling of the object upon or after formation, cohesive failure of thesupport structures concurrently built with the object to support theobject during the build process, adhesive failure or breaks betweendifferent materials constituting the object, the formation of stresscracks in the object, and delamination of layers constituting theobject.

Important physical properties of a suitable phase change compositionwhich influence the above include jetting viscosity, thermal stabilityat the jetting viscosity, melting point, softening point and softeningrange, freezing or solidification point, toughness, hardness, tensilestrength and elongation.

A variety of factors influence success or failure at different stages ofthe build process. Initially, various constraints are imposed at thedispensing or jetting point of the process. It is currently eminentlydesirable to increase the existing deposition rates of buildcompositions, i.e. to significantly increase the jetting rate or speedof deposition of the build compositions, which requires compositionsthat are thermally stable and low in viscosity at high temperatures.During the build process itself, it is important to avoid curling,cracking and delamination of the multi-layered object as it forms andsolidifies layer-by-layer. Finally, it is important to provide afinished three-dimensional article having the requisite toughness suchthat the product does not break or crumble easily with handling and use.

Phase change compositions useful in building three-dimensional objectsby selective deposition modeling must have an appropriate viscosityrange at the temperature range at which jetting or deposition takesplace, taking into account the particular ink jet print head used in thebuild apparatus. Such compositions must also have an appropriate meltingpoint range and freezing point range within the temperature range usedin the build process so as to expedite the build process whilesimultaneously avoiding the development of defects in the object beingbuilt.

There is a variety of challenges peculiar to building three-dimensionalobjects by selective deposition modeling. It is desirable to minimize orcompletely avoid each of these problems. Cohesive failure is one suchproblem. Cohesive failure is a break within the material itself afterdeposition and solidification. Adhesive failure is another concern.Adhesive failure is a break at the interface between different materialsafter deposition and solidification. Curl is a particularly vexingdefect. Curl is the lifting of a deposited multi-layered object in theZ-direction, either during or after solidification, due to largedifferences in shrinkage stress transmitted from layer to layer of thedeposited material. Typically, from about 10% to about 15% shrinkage canbe observed in other selective deposition modeling compositions betweenthe time of dispensing (dispensing or jetting temperature) and finalformation of the multi-layered object (ambient or solid temperature).Such high shrinkage rates are unacceptable, since they result in severedefects in the formed object, including not only curl, but also stresscracks and delamination of object layers.

Stress cracking is fracturing of a multi-layered object in either theX-axis (Y-Z plane), or Y-axis (X-Z plane), during or aftersolidification, due to high shrinkage stress from layer to layer of theobject, low cohesive strength of the material itself and/or the specificgeometry of the object being built. Delamination is the separation oflayers of an object in the Z-axis (X-Y plane) due to differences in thesurface energy of deposited and solidified solid portions of the objectand the surface tension of molten material being deposited onto thosesolid portions. Thermal meltdown, also known as thermal runaway, is yetanother concern. Thermal runaway is the melting of deposited objectlayers into a puddle of liquid, which can result from a detrimentallylow freezing point (solidification point) for the phase changecomposition.

The selective deposition modeling of three-dimensional objects hasheretofore involved one or more of the above-described deficiencies tovarying degrees. Phase change compositions used thus far in theselective deposition modeling of three-dimensional objects have provedlacking in terms of their optimal physical properties and the requisitetoughness, hardness, elongation and lack of curl, crack and delaminationof the finished objects. While a plethora of phase change compositionshave been designed as hot melt ink compositions for two-dimensionalprinting, as disclosed for example in U.S. Pat. No. 4,889,560 to Jaeger,et al. issued Dec. 26, 1989, and U.S. Pat. No. 4,830,671 to Frihart etal. issued May 16, 1989, such compositions do not possess the requisiteproperties for successfully building three-dimensional objects byselective deposition modeling.

It is thus highly desirable and would be a significant advance in theart to develop phase change compositions that not only result inthree-dimensional objects devoid of the above-described undesirabledefects, but that also permit a significantly more rapid building ofsuch objects than has heretofore been achieved.

Ranges and ratios may be combined and are by weight unless otherwiseindicated. Temperatures are in degrees Celsius. unless otherwiseindicated. All references to published information are hereinincorporated by reference.

SUMMARY OF THE INVENTION

The present invention provides improved phase change compositions forselective deposition modeling techniques used in buildingthree-dimensional objects. The present invention provides improved phasechange compositions for use in selective deposition modeling techniquesfor building three-dimensional objects that facilitate the use ofincreased jetting and deposition rates for the compositions, coupledwith rapid solidification of the compositions after jetting anddeposition.

The present invention further provides improved compositions for use inselective deposition modeling techniques for building three-dimensionalobjects having higher freezing and melting temperatures that solidifyquickly after deposition and are not subject to thermal meltdown. Stillfurther, the present invention provides improved phase changecompositions for use in selective deposition modeling techniques forbuilding three-dimensional objects possessing minimal shrinkagecharacteristics.

The present invention additionally provides improved phase changecompositions for use in building three-dimensional objects by selectivedeposition modeling techniques that result in three-dimensional objectsthat do not have undesired curl and stress cracks or are subject todelamination of the various layers of the objects. The present inventionmoreover provides improved phase change compositions for use inselective deposition modeling techniques that provide superiortoughness, hardness and elongation properties in three-dimensionalobjects built from such compositions. The present invention yet furtherprovides phase change compositions that result in three-dimensionalobjects formed by selective deposition modeling techniques that are notbrittle, but rather are characterized by a superior elongation andductility than hitherto known three-dimensional objects formed by suchprocesses.

In a further aspect of the present invention, there are providedselective deposition modeling methods for building three-dimensionalobjects on a layer-by-layer basis that employ superior compositions asbuild materials for such objects.

A phase change composition of the present invention that is a solid atambient temperature and a liquid at an elevated temperature aboveambient temperature, adapted for use in selective deposition modeling toform a three-dimensional object, comprises a semi-crystalline mixture ofpolar and non-polar components, the semi-crystalline mixture having afreezing point of at least about 68° C., a melting point of at leastabout 88° C., and a viscosity of about 13 centipoise at about 135° C. Asused in this specification in relation to the phase change compositionsof the present invention, the term “ambient temperature” refers totypical room temperatures of about 20° C. to about 25° C.

The present invention also provides a phase change composition that is asolid at ambient temperature and a liquid at an elevated temperatureabove ambient temperature comprising a semi-crystalline mixture ofcomponents including a tetra-amide and a plurality of waxes, theplurality of waxes having a melting point range from about 85° C. toabout 130° C. and a molecular weight range from about 150 to about 5000.

The wax components of the phase change composition are viscositymodifiers. The plurality of waxes possesses low viscosity, a broadmelting point range, a broad molecular weight range and low shrinkageupon cooling. A particularly preferred melting point range for theplurality of waxes is from about 80° C. to about 110° C. and a preferredmolecular weight range is from about 200 to about 3000. The waxes havemelting points in the range selected from the group consisting of: 86°C. to 90° C., 91° C. to 94° C., or 90° C. to 97° C., and 104° C. to 116°C. In this regard, each wax has a melting point and a molecular weightthat is different from each of the melting points and molecular weightsof each of the remaining waxes. Each wax has a melting point and amolecular weight that falls within the specified range.

In yet another preferred aspect of the present invention, a phase changecomposition for selective deposition modeling of three-dimensionalobjects comprises a semi-crystalline mixture of components including atetra-amide, a mono amide wax, at least one wax selected from the groupconsisting of petroleum waxes and synthetic waxes to minimize shrinkageof the formed object, and a first tackifier to increase toughness of theformed object. Preferably, the first tackifier is a modified rosinester, and more particularly a tri-ester of hydrogenated abietic acidwith glycerol.

In another preferred aspect of the present invention, there is provideda phase change composition for selective deposition modeling ofthree-dimensional objects comprising a semi-crystalline mixture ofcomponents including a tetra-amide, a first tackifier to increasetoughness of the composition and a second tackifier to increase hardnessof the composition. Preferably, the first tackifier is a modified rosinester and the second tackifier is a hydrocarbon based aromatic resin.

The present invention further provides a phase change composition foruse in selective deposition modeling of three-dimensional objectscomprising a semi-crystalline mixture of components including atetra-amide; a mono-amide wax; and at least one ester component forhydrogen-bonding with the tetra-amide and the mono-amide wax, therebyincreasing the toughness of the composition. Preferably, the estercomponent comprises an ester tackifier and an ester plasticizer forincreasing both the toughness and ductility of the composition.

In a particularly preferred embodiment of the present invention, a phasechange composition for selective deposition modeling ofthree-dimensional objects comprises a semi-crystalline mixture ofcomponents including a tetra-amide, a mono-amide wax, a petroleum wax, apolyethylene wax, an ethylene-propylene copolymer wax, a modified rosinester, a hydrocarbon based aromatic resin, an alkyl benzene phthalate,at least one antioxidant and at least one colorant.

In yet another aspect of the present invention, a selective depositionmodeling method for forming a three-dimensional object on alayer-by-layer basis employs a phase change composition formulated inaccordance with the present invention. The method comprises providingthe phase change composition as a building material for athree-dimensional object; elevating the temperature of the buildingmaterial to a temperature sufficient to cause the material to becomefluid; selectively dispensing the material at the elevated temperatureto form a layer of the material as a cross-section of thethree-dimensional object, and lowering the temperature of the dispensedmaterial to at least partially solidify the material.

In yet another aspect of the present invention, there is provided amethod of making a phase change composition for use in the selectivedeposition modeling of three-dimensional objects.

DETAILED DESCRIPTION OF THE INVENTION

Selective deposition modeling compositions for forming three-dimensionalobjects in accordance with the present invention contain, in variouspreferred embodiments, an array of individual polar and non-polarcrystalline and amorphous components that will now be described indetail. The various components are combined prior to use into asemi-crystalline phase change mixture having diverse properties that areimportant to the successful selective deposition modeling ofthree-dimensional objects. The semi-crystalline phase change mixturealso is substantially homogeneous.

The tetra-amide component of the compositions of the present inventionis a low molecular weight amorphous, polar polymer or oligomer that hasa low viscosity to facilitate jettability during the object buildprocess. Suitable tetra-amides for use in the present invention aredisclosed, for example, in U.S. Pat. No. 4,830,671 to Frihart et al.issued May 16, 1989, U.S. Pat. No. 5,194,638 to Frihart et al. issuedMar. 16, 1993, U.S. Pat. No. 4,889,560 to Jaeger, et al. issued Dec. 26,1989, and U.S. Pat. No. 5,645,632 to Pavlin issued Jul. 8, 1997, thecontents of which are incorporated herein by reference.

Typical tetra-amides useful in the present invention, as disclosed forexample in U.S. Pat. No. 4,830,671 to Frihart et al. issued May 16,1989, are represented by the following formula:

R₄—CONH—R₂—NHCO—R₁—CONH—R₃—NHCO—R₅

wherein R₁ is a polymerized fatty acid residue with 2 carboxylic acidgroups removed; R₂ and R₃ are the same or different and each representsan alkylene with up to 12 carbon atoms, a cycloalkylene with 6 to 12carbon atoms, an arylene with 6 to 12 carbon atoms, or an alkarylenewith 7 to 12 carbon atoms; and R₄ and R₅ are the same or different andeach represents an alkyl, a cycloalkyl, an aryl, or an alkaryl with upto 36 carbon atoms.

The tetra-amide typically has a molecular weight in the range of about1294 to about 2162 and a viscosity of less than 250 centipoise at 150°C., typically 50 to 100 centipoise at 150° C. A particularly preferredtetra-amide for use in the present invention is available commerciallyfrom Union Camp Corporation under the designation X37-523-235, which hasa viscosity of 52 centipoise at 150° C. and a softening point of about128° C.

The tetra-amide is a low molecular weight resinous binder having fouramide sites that provide the venue for hydrogen bonding with othercomponents of the formulation. as will be described below, leading toenhanced toughness in the final formed object. The tetra-amideadditionally has a low viscosity to enable jettability of theformulation at high temperatures. The tetra-amide component is presentin the compositions of the present invention in amounts preferablyranging from about 5% to about 30% by weight of the total composition,more preferably ranging from about 10% to about 20% by weight, and mostpreferably in an amount of about 17.61% by weight.

The wax components of the compositions of the present invention functionas viscosity modifiers and are characterized by low viscosity, acollective broad melting point range and low shrinkage. A preferredratio of the combined weight percentages of the waxes to the weightpercentage of the tetra-amide in the formulations of the presentinvention ranges from about 2:1 to about 6:1.

A first wax component of the compositions of the present invention is amono-amide wax. The mono-amide wax component is a secondary amideresulting from the reaction of saturated and unsaturated fatty acidswith saturated and unsaturated primary amines. A variety of compoundsresult, as exemplified by the known compounds stearyl erucamide, erucylerucamide, oleyl palmitamide, stearyl stearamide and erucyl stearamide.

Suitable mono-amides for use in the present invention are known per seand are disclosed, for example. in U.S. Pat. No. 4,889,560 to Jaeger, etal. issued Dec. 26, 1989, and U.S. Pat. No. 5,372,852 to Titterington etal. issued Dec. 13, 1994, the contents of which are incorporated hereinby reference. Typical mono-amides useful in the present invention, asdisclosed for example in U.S. Pat. No. 4,889,560 to Jaeger, et al.issued Dec. 26, 1989, are represented by the following formula:

C_(X)H_(Y)—CONH—C_(A)H_(B)

wherein X is an integer from 5 to 21; Y is an integer from 11 to 43; Ais an integer from 6 to 22; and B is an integer from 13 to 45.

The mono-amide typically has a molecular weight in the range of about199 to 647 and a viscosity ranging from about 1 to about 15 centipoiseat 135° C. A particularly preferred mono-amide for use in the presentinvention is stearyl stearamide, available commercially, for example,from Witco Corporation under the designation Kemamide S-180. KemamideS-180 has a viscosity of about 5.9 centipoise at 135° C. and a meltingpoint ranging from about 92° C. to about 95° C.

The hydrocarbon, stearyl groups at each end of the secondary mono-amideprovide it with a crystalline, waxy nature. The short carton chainlength gives the mono-amide a desired low melt viscosity. Nevertheless,the mono-amide is sufficiently non-polar to solubilize waxy, hydrocarboncomponents in the formulation. The secondary amide group at the coreprovides the requisite polarity to make it compatible with polarcompounds in the formulation, for example, the tetra-amide and, as willbe described below, the ester tackifier and ester plasticizer. The amidegroup in the secondary mono-amide increases the melting point, whichhelps the formulation in terms of providing a higher freezing point,which in turn results in quick solidification of the formulation afterdispensing. Finally, the amide site of the mono-amide also provides thevenue for hydrogen bonding with other components of the formulation, aswill be described below, leading to enhanced toughness in the finalobject formed.

Overall, then, the mono-amide is a polar component of the formulation ofthe present invention acts as a viscosity modifier for the formulationand a co-solubilizer of polar and non-polar components in theformulation, while possessing both a desirably high and sharp meltingpoint and low viscosity. That is, the mono-amide has sufficientnon-polar hydrocarbon properties to solubilize non-polar materials eventhough it is classed as a polar compound.

The mono-amide component is present in the compositions of the presentinvention in amounts preferably ranging from about 15% to about 40% byweight of the total composition, more preferably from about 20% to about30% by weight, and most preferably in an amount of about 26.91% byweight. A preferred ratio of the weight percentage of the mono-amide tothe weight percentage of the tetra-amide in the formulations of thepresent invention ranges from about 4:1 to about 1:1.

A second wax component of the compositions of the present invention is apetroleum wax. Petroleum waxes are a class of petroleum waxes that areproduced in known manner by the solvent recrystallization of selectedpetroleum fractions into materials consisting of n-paraffinic, branchedparaffinic and naphthenic hydrocarbons in the C₃₀ to C₆₀ range.

Petroleum waxes suitable for use in the present invention are known.They typically have molecular weights ranging from about 422 to about842 and melting points ranging from about 88° C. to about 96° C. Aparticularly preferred petroleum wax for use in the present invention isavailable commercially from Baker Petrolite Corporation under thedesignation C-700, has a melting point of about 93° C. and has aviscosity of about 8.6 centipoise at 135° C.

The petroleum wax component is present in the compositions of thepresent invention in amounts preferably ranging from about 5% to about25% by weight of the total composition, more preferably from about 10%to about 20% by weight, and most preferably in an amount of about 16.63%by weight. The petroleum wax has the dual functions of increasing thehardness and reducing the shrinkage of the final formulation.

A third wax component of the compositions of the present invention is apolyethylene wax. Such synthetic waxes are known per se, belong to thefamily of fully saturated crystalline homopolymers of ethylene, and arecharacterized by unusually narrow melt distribution, low meltviscosities and extreme hardness at elevated temperatures. They exhibitoutstanding heat stability and resistance to chemical attack due tobeing fully saturated.

Polyethylene waxes suitable for use in the present invention typicallyhave molecular weights ranging from about 500 to about 3000 and meltingpoints ranging from about 80° C. to about 129° C. A particularlypreferred polyethylene wax for use in the present invention is availablecommercially from Baker Petrolite Corporation under the designation PEW500, or Polywax 500. which has a melting point of about 88° C. and aviscosity of about 4.1 centipoise at 135° C.

The polyethylene wax component is preferably present in the compositionsof the present invention in amounts ranging up to about 15% by weight ofthe total composition, conveniently from about 3% to about 10% byweight, preferably about 4% to about 9%, and most preferably in anamount of about 5.87% by weight. A preferred ratio of the weightpercentage of the petroleum wax to the weight percentage of thepolyethylene wax in the formulations of the present invention rangesfrom about 3:1 to about 1:1. The hard polyethylene wax is used in theformulation of the present invention because of its outstanding thermalstability, high hardness and high melting point.

A fourth wax component of the compositions of the present invention is asynthetic branched wax. Particularly useful synthetic branched waxes foruse in the present invention include synthetic microcrystalline analogsof polywax, such as ethylene-propylene copolymers, which are moreconsistent and reproducible than the petroleum derived waxes. Such waxesexhibit desirable flexibility at low temperatures.

Ethylene-propylene copolymer waxes suitable for use in the presentinvention typically have molecular weights ranging from about 650 toabout 1200 and melting points ranging from about 96° C. to about 112° C.A particularly preferred ethylene-propylene copolymer wax for use in thepresent invention is available commercially from Baker PetroliteCorporation under the designation EP 1100 which has a melting point ofabout 110° C. and a viscosity of about 17.6 centipoise at 135° C.

The synthetic branched wax component is preferably present in thecompositions of the present invention in amounts ranging up to about 10%by weight of the total composition preferably about 1% to about 6% byweight, more preferably from about 2% to about 5% by weight, and mostpreferably in an amount of about 2.94% by weight. A preferred ratio ofthe weight percentage of the polyethylene wax to the weight percentageof the synthetic branched wax in the formulations of the presentinvention ranges from about 3:1 to about 1:1. The synthetic branched waxis used in the formulation of the present invention because of its highmelting point and low temperature flexibility. The branching from, forexample, the propylene group in the ethylene-propylene copolymer waxhelps minimize shrinkage of the formulation.

Optionally, the formulations of the present invention may include anester wax in amounts typically up to about 10% by weight of the totalcomposition, and more preferably in amounts of about 1% to about toabout 5% by weight, more preferably about 1.5% to 4.5% by weight. Aparticularly preferred ester wax for use in the present invention isavailable commercially from Floechst Corporation under the designationWax E. Wax E is an ester wax derived from Montan wax and has a molecularweight range of from about 730 to about 750, a viscosity of 14.5centipoise at 130° C. and a melting point of about 77.34° C. The esterwax increases the hardness of the formulations of the present invention.In this regard, the ester wax provides a synergistic effect on thehydrogen bonding that occurs in the formulation, as will be discussed inmore detail below, and also favorably affects the formulation's heatstability.

Each wax in the formulations of the present invention has a differentmelting point than each of the remaining waxes in the formulation. Thedistribution of melting points of the various waxes in the compositionsof the present invention provides a formulation having a largetemperature transition from a liquid to a solid state after deposition,which minimizes shrinkage in the deposited material. This broadtransition gives the deposited material time to relax and minimizesinternal stresses which build up due to shrinkage of the material duringcooling, which stresses would be much greater if the material solidifiedquickly at or about a single temperature.

The first tackifier component of the compositions of the presentinvention is a modified rosin ester. Such rosin esters are highlypurified for use where extremely low metallic content is needed, as wellas low odor, taste and water white color. Particularly useful rosinesters for use in the present invention include trimesters ofhydrogenated abietic acid with glycerol, which are known per se, asdisclosed in U.S. Pat. No. 4,889,560 to Jaeger, et al. issued Dec. 26,1989 and U.S. Pat. No. 5,372,852 to Titterington et al. issued Dec. 13,1994, the contents of which are incorporated herein by reference.

A particularly preferred tri-ester tackifier for use in the presentinvention is available commercially from Arakawa Chemical, Inc. underthe designation KE-100. KE-100 has a molecular weight of about 962, asoftening point of about 102.97° C.±0.88° C., a softening point rangefrom about 66° C. to about 110° C. and a viscosity in a 50/50 mixturewith the mono-amide wax component of about 15.2 centipoise at 135° C.The first tackifier component is present in the compositions of thepresent invention in amounts conveniently ranging from about 10% toabout 40% by weight of the total composition, more preferably about 12%to about 35% by weight, even more preferably from about 15% to about 30%by weight, and most preferably in an amount of about 16.63% by weight. Apreferred ratio of the weight percentage of the ester tackifier to theweight percentage of the tetra-amide in the formulations of the presentinvention ranges from about 0.5:1 to about 5:1. A preferred ratio of thecombined weight percentages of the tetra-amide and the mono-amide wax tothe weight percentage of the ester tackifier in the formulations of thepresent invention ranges from about 1:1 to about 3:1.

The ester tackifier interacts with both the tetra-amide and themono-amide wax to synergistically increase the toughness of the finalformed object. In this regard, an intermolecular attraction between theunsaturated oxygen atoms of the (polar) ester tackifier and the hydrogenatoms at the amide sites of the tetra-amide and the mono-amide wax,generally known in the chemical field as hydrogen bonding, provides thissynergistic increase in toughness.

A second tackifier component of the compositions of the presentinvention is a hydrogenated hydrocarbon based aromatic resin. Thenon-polar hydrocarbon hydrogenated based aromatic resin is compatiblewith the waxes in the formulation and increases the hardness of theformulation. The increased hardness decreases cohesive and adhesivefailure between the material of the formed object and the material ofthe support structures for the object, which in turn facilitatessubsequent removal of the support structures from the final formedobject.

Hydrocarbon based aromatic resins suitable for use in the presentinvention are manufactured in known manner by the selective partialhydrogenation of based resins that have been polymerized from mixedaromatic monomer feed streams. They typically have molecular weights inthe range of from about 700 to about 1300 and softening points in therange from about 90° C. to about 125° C. A particularly preferredhydrocarbon based aromatic resin for use in the present invention isavailable commercially from Hercules under the designation RegaliteR101. Regalite R101 has a molecular weight of about 850, a softeningpoint of about 99° C. and a viscosity in a 50/50 mixture with themono-amide wax component of about 17.8 centipoise at 135° C.

The hydrocarbon based aromatic resin is preferably present in thecompositions of the present invention in amounts ranging up to about 15%by weight of the total composition, more preferably from about 5% toabout 12% by weight, and most preferably in an amount of about 9.1% byweight. A preferred ratio of the combined weight percentages of thehydrocarbon waxes to the weight percentage of the hydrocarbon basedtackifier in the formulations of the present invention ranges from about2:1 to about 3:1. In this regard, the hydrocarbon waxes include thepetroleum wax, the polyethylene wax, the synthetic branched wax and theester wax, but do not include the mono-amide wax.

The second tackifier is used in the formulation of the present inventionto increase the hardness of the formulation. This facilitates removal ofthe various support structures from the surfaces of the final formedobject.

The plasticizer component of the compositions of the present inventionis a polar compound chosen to help increase elongation and decrease themodulus of elasticity, thus decreasing brittleness and correspondinglyincreasing flexibility of the final formed object. Benzyl phthalates,and preferably alkyl benzene phthalates (such as mixed esters), havebeen found to be particularly suitable for these purposes.

A particularly preferred plasticizer for use in the present invention isavailable commercially from Monsanto under the designation Santicizer278. Santicizer 278 is a liquid high molecular weight benzyl phthalatepossessing low volatility, excellent permanence and aggressive solvatingcharacteristics, with a molecular weight of about 455 and a viscosity ofabout 5.2 centipoise at 135° C. The plasticizer is present in thecompositions of the present invention in amounts preferably ranging upto about 10% by weight of the total composition, more preferably fromabout 2% to about 6% by weight, and most preferably in an amount ofabout 3.91% by weight. A preferred ratio of the weight percentage ofamide (tetra-amide plus mono-amide wax) to the weight percentage ofester (ester tackifier plus ester plasticizer) in the formulations ofthe present invention ranges from about 0.75:1 to about 2.5:1.

The plasticizer is used in the formulation of the present invention toincrease the elongation and decrease the modulus of elasticity of thefinal formed object. An elongation of up to about 73%, advantageouslyranging from about 14% to about 200%, is achievable using theformulations of the present invention. This decreases brittleness of thefinal formed object, providing an object that is more ductile thanheretofore known in the art. This increased ductility facilitates parthandling of thin wall features of the final formed object and providesan object less subject to curl, crack and delamination. The esterplasticizer also provides additional ester sites for hydrogen bondingwith the amide sites of the tetra-amide and the mono-amide wax, thusfavorably influencing the toughness of the formulation.

The compositions of the present invention preferably include at leastone antioxidant. A primary antioxidant can be used in the formulationsof the present invention as a free radical scavenger. A secondaryantioxidant can be used in the formulations of the present invention asan alkyl hydroperoxide scavenger.

The primary and secondary antioxidants are each present in theformulation in amounts preferably less than about 1% by weight of thetotal formulation and, most preferably in amounts of about 0.2% byweight. A particularly preferred free radical scavenger antioxidant foruse in the present invention is available commercially from UniroyalChemical Co., Inc. under the designation Naugard 524. A particularlypreferred alkyl hydroperoxide scavenger antioxidant for use in thepresent invention is 4,4′-bis(alpha, alpha-dimethylbenzyl)diphenylamine,available commercially from Uniroyal Chemical Co., Inc. under thedesignation Naugard 445. Naugard 445 has a molecular weight of about 405and a melting point of about 98° C. to about 100° C.

The formulations of the present invention optionally include at leastone colorant. In this regard, the colorant is preferably a solvent dye.Virtually any acid dye, dispersed dye, or solvent dye or combinationthereof may be employed in the compositions of the present invention. Aparticularly preferred solvent dye is available commercially fromClariant Corporation under the designation Savinyl Black RLS, which is atrivalent chromium complex of an azo dye known as C.I. Solvent Black 45.

The colorant can be present in the formulation in any desired amount.However, an excessive amount of colorant in the formulation reducesfiltration efficiency not only during the formulation manufacturingprocess, but also during jetting from the print head during objectbuilding. Accordingly, the colorant is preferably present in an amountno greater than about 2% by weight of the total composition, morepreferably in an amount no greater than about 1% by weight. and mostpreferably in an amount of about 0.09% by weight. As little as about0.001% by weight of colorant may be used in the formulations of thepresent invention. In this regard, large quantities of colorant are notneeded in the formulations of the present invention to effectively colorthe object built.

The phase change compositions of the present invention possess manyadvantages in comparison to phase change compositions used heretofore inthe selective deposition modeling of three-dimensional objects. Theincreased freezing point of the formulation, at least 68° C., increasesthe temperature delta or differential between ambient temperature andthe freezing point in comparison to the most advanced knownformulations, which possess freezing points of about 56° C. Thisincreased temperature differential allows the deposited liquid materialto solidify more quickly after deposition than previously possible. Theincrease in solidification rate permits the use of significantly fasterdeposition rates of the molten material during the build process thanhitherto achievable. As a consequence, three-dimensional objects can nowbe built much more quickly using selective deposition modeling methodsby employing a significantly faster build speed coupled with asubstantially quicker solidification of the deposited melted material.

The decreased viscosity of the formulation, of less than 18 centipoise,and preferably about 13 centipoise at 135° C., allows for optimumjetting performance using preferred ink jet print heads, which aredesigned for optimum performance when used in conjunction with phasechange materials having a viscosity of 13 centipoise at 135° C.

The formulations of the present invention are characterized by superiorthermal stability in relation to known formulations. The compositions ofthe present invention demonstrate a viscosity increase of only 18% afterbeing thermally aged for 28 days at 140° C., in comparison to knownthree-dimensional modeling compositions, which are characterized byviscosity increases of up to 48.1% under similar conditions.

The combination of waxes defining broad molecular weight and meltingpoint ranges provides a formulation with lower shrinkage, which resultsin three-dimensional objects having reduced curl. In a particularlypreferred embodiment, curl is optimally reduced-by formulating the phasechange composition with a combination of four waxes. Each wax has adifferent melting point within the range from about 88° C. to about 110°C. and a different molecular weight within the range from about 200 toabout 3000.

The combination of amide and ester components in the formulations of thepresent invention leads to enhanced toughness in the finishedthree-dimensional objects over that obtained by previous selectivedeposition modeling methods for building three-dimensional objects.Thus, the intermolecular attraction between the amides of theformulation, i.e., the tetra-amide and the mono-amide wax, and theesters of the formulation, i.e., the rosin ester tackifier and/or theester plasticizer, results largely from hydrogen bonding between thesecomponents, which results in a tougher final product than heretoforeknown.

The formulations of the present invention are also characterized bysuperior ductility in relation to known formulations. The compositionsof the present invention demonstrate an advantageous Elongation rangingfrom at least about 14% to about 73% and a Flex Modulus that result inan extremely flexible material that is less brittle, and less subject tocurl, stress crack and delamination, than other materials. In turn, easeof removal of the support structures from the finished three-dimensionalobject is enhanced and simplified.

The phase change compositions of the present invention can be used tobuild superior three-dimensional objects. In this regard, thecompositions of the present invention are especially suitable forbuilding three-dimensional objects of substantial size, e.g., objectshaving a minimum height of at least 1 cm., measured in the Z-direction.

EXAMPLE 1

A formulation is made in accordance with the present invention by mixingthe individual components in a kettle equipped with a mixing blade andpreheated to 115° C. The mixture is heated at 115° C. after the additionof each component with moderate stirring, for example at 5 RPM, until ahomogenized, molten state is achieved. The next component is then addedand the heating and melting steps repeated.

TABLE 1 Component Melting Pt. (° C.) Weight % PEW 500 88 5.87 C 700 9616.63 Naugard 445 99 0.2 X37-523-235 128 17.61 Naugard 524 — 0.2Santicizer 278 Liquid 3.91 KE-100 66.73 16.63 Regalite R101 100 9.1 EP1100 110.46 2.94 Kemamide S-180 93.7 26.91

After components are mixed and melted, the formulation is heated furtherfor 1 hour at 115° C. with mixing at 60 RPM, followed by mixing at 10RPM, until a uniform liquid is obtained. The formulation is then testedfor viscosity, after which 0.09 weight % of a colorant, Savinyl RLSBlack, is added. The formulation is mixed again at 60 RPM for 1 hour at115° C. The final homogeneous formulation is then tested again to assurea final desired viscosity.

The above formulation has the physical properties shown in the followingTable 2:

TABLE 2 Jetting Temperature (° C.) 135° C. Viscosity (Centipoise)  13.0± 0.3 at 135° C. Hardness (Shore D)  45 Elongation (% E)  73 FlexModulus (MPa) 230 Surface Tension (dyne/cm)  32 Density (g/ml)  0.86Melting Point (° C.)  88° C. Freezing Point (° C.)  68° C. Work(in-lb/in³)  12 Stress Yield (MPa)  3

EXAMPLES 2 TO 7

A variety of formulations are made in accordance with the presentinvention in the same manner as set forth in Example 1. The compositionsare formulated as shown in the following Table 3, wherein amounts ofeach component of the formulation are indicated as percentages by weightof the total formulation:

TABLE 3 Component Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Kemamide 25.5 30.825.5 25.8 23 26 S180 C700 17 9 17 17 17 21 PEW500 6 6 6 6 9 0 EP1100 3 33 3 0 2 Wax E 0 0 0 0 0 5 Santicizer 278 4 6 4 4 4.8 4.5 KE100 17 3627.3 23 23 21.3 Regalite R101 9.3 0 0 0 0 0 X-37-523-235 18 9 17 21 2320 N524 0.2 0.2 0.2 0.2 0.2 0.2

Three-dimensional objects are made using a selective deposition modelingmethod employing the formulations of Examples 2 to 7. The formulationsare selectively deposited onto the building platform of athree-dimensional modeling system layer-by-layer using an ink jet printhead manufactured by Tektronix, Inc. designed for optimum jettingperformance for phase change compositions having a viscosity of 13centipoise at 135° C. The materials are very tough, flexible and notsubject to thermal meltdown during the high temperature build process,as demonstrated by tests conducted to measure various criticalproperties of the formulations and objects built using thoseformulations.

Hardness of the three-dimensional object is measured using the ASTMD2240-95 (Shore D) standard test for measuring durometer hardness. Thistest measures penetration into the object by a specific type ofindentor, PTS instrument Model 409. Toughness of the three-dimensionalobject is defined as the integration of the area under the stress straincurve for the material (Work) and is measured, along with Stress Yield(MPa) and Elongation (%), using the ASTM D638-87a standard test formeasuring tensile properties. The Flex Modulus of the three-dimensionalobject is measured using the ASTM D790-97 standard test for flexuralproperties (MPa).

Physical properties of the formulations. as well as the physicalproperties of three-dimensional objects made therefrom, are indicated inthe following Table 4:

TABLE 4 Physical Property Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Viscosity@ 12.9 12.9 13 13.4 13.2 13.3 135° C. Hardness 45 46 45 44 43 43 (ShoreD) Melting Point 90 88 89 91 91 91 (° C.) Freezing Point 69 69 68 68 7171 (° C.) Work (in-lb/ 11.8 12 13.5 9.8 2.9 5.2 in³) % Elongation 14 7323 9 3 4 Stress Yield 3 2.2 3 3 2.8 3.8 (MPa) Flex Modulus 218 185 222** 230 ** (MPa) Qualitative Tough Hard Tough Tough Tough Tough Result

COMPARATIVE EXAMPLE

A hot melt ink composition disclosed in U.S. Pat. No. 4,889,560 toJaeger, et al. issued Dec. 26, 1989 for two-dimensional printing isformulated with a tetra-amide, a mono-amide, a tackifier, a plasticizerand an antioxidant. The composition is formulated as shown in thefollowing Table 5, wherein amounts of each component are indicated aspercentages by weight of the total formulation:

TABLE 5 Component Weight % Kemamide S-180 48 X-37-523-235 20.8 KE-100 23Santicizer 278 8 N-524 0.2

The composition is employed to make a three-dimensional object byselective deposition modeling, in the same manner as the formulations ofExamples 2 to 7. The properties of the composition, measured in the samemanner as in Examples 2 to 7, are enumerated in the following Table 6:

TABLE 6 Jetting Temperature (° C.) 135° C. Viscosity (Centipoise) 13 at135° C. Hardness (Shore D) 37 Melting Point (° C.) 91 Freezing Point (°C.) 71 Work (in-lb/in³) 3.8 % Elongation 6 Stress Yield (MPa) 2 SurfaceTension (dyne/cm) 29.53 Density (g/ml) 0.85 Flex Modulus (MPa) 176

Three-dimensional objects manufactured using the phase change ink of theComparative Example and using the phase change formulations of Examples2 to 7 according to the present invention are subjected to processevaluation at a room temperature of 260 C. to determine curl, crack anddelamination characteristics. The results of the process evaluation areindicated in the following Table 7:

TABLE 7 C. Ex. Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Left Curl (mm) 2.71.5 1.5 1.5 2 2 2.5 Right Curl (mm) 2.7 1.5 1.5 1.5 2 2 2.5 Crack (mil)50 50 None None None None None Delamination 14 20 23 18 18 16 18 (MLS)Support Average Easy Easy Easy Easy Easy Gummy Removal Thermal 13,13,813,13,9 13,13,8 13,13,9 13,13,8 13,13,9 13,13,9 Runaway

Curl is determined by building a set of four bars of 252×6 mm withincreasing thickness of 1, 2, 4, and 8 mm. Each of Examples 2 to 7 andthe Comparative Example is built using an Actua 2100 Concept Modeler, athree-dimensional modeling apparatus available from 3D Systems, Inc. ofValencia, Calif. The amount by which the left and right ends of eachblock raise up off the build platform 24 hours after the build iscompleted is then measured. The block is also examined at this time forany cohesive or adhesive failure, including failure at the interfacebetween the build platform and the block, failure within the supportstructures for the object, and failure at the solid interface betweenthe object and the support structures for the object.

It will be observed from Table 7 that all formulations of the presentinvention result in three-dimensional objects characterized by reducedcurl (as little as 1.5 mm) in relation to three-dimensional objectsbuilt attempting to use a two-dimensional printing phase changecompositions, i.e., using the formulation of the Comparative Example(left and right curl of 2.7 mm). This is a significant advance in theselective deposition modeling production of desirable three-dimensionalobjects.

Additionally, three-dimensional objects built using the formulations ofthe present invention are generally notable for their absence of stresscracks. Three crack diagnostic bars of 50 mil (1.27 mm), 75 mil (1.91mm) and 100 mil (2.54 mm) of varying widths are built using an Actua2100 Concept Modeler for each of the formulations of Examples 2 to 7 andthe Comparative Example. Each bar is examined for cracks immediatelyafter the build and 24 hours after completion of the build. Ameasurement of “none” indicates that no cracks are observed in any ofthe three bars. A measurement of “50” indicates that cracks are observedin the 50 mil (1.27 mm) bar, but not in the other bars. As can be seenfrom Table 7, the tested formulations of the present invention generallyresult in bars of 50 mil (1.27 mm), 75 mil (1.91 mm) and 100 mil (2.54mm) having no observable cracks at all, while the 50 mil (1.27 mm) barof the Comparative Example cracks.

The formulations of the present invention also result in supportstructures that are not characterized by cohesive failure. A fractalsupport is used to evaluate the ease of support removal, 30 minutesafter the object build is complete. The strong cohesiveness of thesupport structures results in their easy and complete removal after thebuild process from the three-dimensional objects they support during thebuild process. Removal of the support structures from thethree-dimensional object of the Comparative Example is problematic andtypical of the difficulty of cleanly and easily removing supportstructures experienced in using a two-dimensional ink formulation forthree dimensional modeling.

The formulations of Examples 2 to 7 and the Comparative Example are alsotested for thermal runaway. A thermal test block of each formulation isbuilt using an Actua 2100 Concept Modeler to a size of 3×1.25×1 inch(7.62×3.18×2.54 cm) with square holes that run vertically through theblock. Thirteen approximately 0.254 mm holes are built into the leftportion of the block, thirteen approximately 0.254 mm holes are builtinto the right portion of the block, and nine holes of various sizesranging from about 0.254 mm to about 2.3 mm are built into the centralportion of the block. The reported data indicates the number of holes onthe left, right and middle, respectively, that are built successfully oneach block. A hole is successfully built if light passes through it. Itwill be seen from the results shown in Table 7 that the formulations ofExamples 2, 4, 6 and 7 resulted in blocks in which all the holes weresuccessfully built (13, 13, 9). Conversely, the formulation of theComparative Example resulted in a block with a hole in the centralportion that had deteriorated due to thermal meltdown (13, 13, 8).

Finally, the formulations of the present invention result inthree-dimensional objects not subject to delamination. A minimum layersecond (MLS) test is used to visually evaluate delamination of a3×1.25×1 inch (7.62×3.18×2.54 cm) thermal diagnostic block built with asingle pass build style (single layer thickness of about 0.0015 mil)(3.8×10−3 cm) using an Actua 2100 Concept Modeler. Under suchconditions, an MLS of at least 16 is necessary to insure thatdelamination will not occur. As can be seen from Table 7. theformulations of the present invention all had MLS values of at least 16,whereas the formulation of the Comparative Example had an MLS value of14, which is insufficient to prevent delamination and typical of atwo-dimensional ink formulation.

While the present invention has been disclosed and described withrespect to particular and preferred embodiments, various modificationsand alternatives will be apparent and will suggest themselves to thoseor ordinary skill in the art. Such modifications and alternatives do notdepart from and are within the spirit and scope of the presentinvention, which is only to be limited as set forth in the appendedclaims.

What is claimed is:
 1. A phase change composition that is a solid atambient temperature and a liquid at an elevated temperature aboveambient temperature, adapted for use in selective deposition modeling toform a three-dimensional object, comprising a semi-crystalline mixtureof polar and non-polar components, the semi-crystalline mixture having afreezing point of at least about 68° C., a melting point of at leastabout 88° C., and a viscosity of about 13 centipoise at 135° C.
 2. Thephase change composition according to claim 1, having a freezing pointin the range of about 68° C. to about 71° C. and a melting point in therange of about 88° C. to about 90° C.
 3. The phase change compositionaccording to claim 1, having an elongation of at least about 14%.
 4. Thephase change composition according to claim 3, having an elongation inthe range of about 14% to about 73%.
 5. The phase change compositionaccording to claim 1, wherein there are at least two waxes present whichhave melting points in the range selected from the group consisting of:86° C. to 90° C., 91° C. to 94° C., or 90° C. to 97° C., and 104° C. to116° C.
 6. The phase change composition according to claim 1, whereinthere are at least three waxes present which have melting points in therange selected from the group consisting of: 86° C. to 90° C., 91° C. to94° C., 90° C. to 97° C., and 104° C. to 116° C.
 7. The phase changecomposition according to claim 1, wherein there are four waxes presentand the melt points of the waxes are in the ranges of 86° C. to 90° C.,and 91° C. to 94° C., and 90° C. to 97° C., and 104° C. to 116° C.
 8. Aphase change composition that is a solid at ambient temperature and aliquid at an elevated temperature above ambient temperature, adapted foruse in selective deposition modeling to form a three-dimensional object,comprising a semi-crystalline mixture of components including atetra-amide and a plurality of waxes, wherein each wax of the pluralityof waxes has a different melting point than each other wax in theplurality of waxes, and each wax has a melting point within the rangefrom about 80° C. to about 135° C.
 9. The phase change compositionaccording to claim 8, wherein each wax of the plurality of waxes has adifferent melting point within the range from about 85° C. to about 130°C.
 10. The phase change composition according to claim 9, wherein thesynthetic wax is selected from the group consisting of polyethylene waxand synthetic branched wax.
 11. The phase change composition accordingto claim 10, wherein the synthetic branched wax is an ethylene-propylenecopolymer wax.
 12. The phase change composition according to claim 8,wherein the ratio of the combined weight percentages of the plurality ofwaxes to the weight percentage of the tetra-amide in the compositionranges from about 2:1 to about 6:1.
 13. The phase change compositionaccording to claim 8, wherein each wax of the plurality of waxes has adifferent molecular weight than each other wax of the plurality ofwaxes, and each wax has a molecular weight within the range from about150 to about
 5000. 14. The phase change composition according to claim8, wherein each wax of the plurality of waxes is selected from the groupconsisting of mono-amide wax, petroleum wax and synthetic wax.
 15. Thephase change composition according to claim 8, wherein there are atleast two waxes in the plurality of waxes which have melting points inthe range of 86° C. to 90° C., and 91° C. to 94° C., and 90° C. to 97°C., and 104° C. to 116° C.
 16. The phase change composition according toclaim 8, wherein there are at least three waxes in the plurality ofwaxes which have melting points in the range of 86° C. to 90° C., and91° C. to 94° C., and 90° C. to 97° C., and 104° C. to 116° C.
 17. Thephase change composition according to claim 8, wherein there are atleast four waxes in the plurality of waxes and the melt points of thewaxes are in the ranges of 86° C. to 90° C., and 91° C. to 94° C., and90° C. to 97° C., and 104° C. to 116° C.
 18. A phase change compositionthat is a solid at ambient temperature and a liquid at an elevatedtemperature above ambient temperature, adapted for use in selectivedeposition modeling to form a three-dimensional object, comprising asemi-crystalline mixture of components including a tetra-amide, amono-amide wax, at least one wax selected from the group consisting ofpetroleum waxes and synthetic waxes, and an ester tackifier.
 19. Thephase change composition according to claim 18, wherein the estertackifier is a modified rosin ester.
 20. The phase change compositionaccording to claim 19, wherein the modified rosin ester is a glyceroltri-ester of hydrogenated abietic acid.
 21. The phase change compositionaccording to claim 18, wherein the ratio of the weight percentage of theester tackifier to the weight percentage of the tetra-amide in thecomposition ranges from about 0.5:1 to about 5:1.
 22. The phase changecomposition according to claim 18, wherein the ratio of the combinedweight percentages of the tetra-amide and the mono-amide wax to theweight percentage of the ester tackifier in the composition ranges fromabout 1:1 to about 3:1.
 23. The phase change composition according toclaim 18, wherein there are four waxes present and the melt points ofthe waxes are in the ranges of 86° C. to 90° C., and 91° C. to 94° C.,and 90° C. to 97° C., and 104° C. to 116° C.
 24. A phase changecomposition that is a solid at ambient temperature and a liquid at anelevated temperature above ambient temperature, adapted for use inselective deposition modeling to form a three-dimensional object,comprising a semi-crystalline mixture of components including atetra-amide, an ester tackifier and a hydrocarbon resin tackifier. 25.The phase change composition according to claim 24, wherein the estertackifier is a modified rosin ester and the hydrocarbon resin tackifieris a hydrocarbon based aromatic resin.
 26. The phase change compositionaccording to claim 25, wherein the modified rosin ester is a glyceroltri-ester of hydrogenated abietic acid.
 27. The phase change compositionaccording to claim 24, wherein the ratio of the weight percentage of theester tackifier to the weight percentage of the tetra-amide in thecomposition ranges from about 0.5:1 to about 5:1.
 28. The phase changecomposition according to claim 24, further comprising a plurality ofwaxes wherein at least two waxes in the plurality of waxes have meltingpoints in the range of 86° C. to 90° C., and 91° C. to 94° C., and 90°C. to 97° C., and 104° C. to 116° C.
 29. The phase change compositionaccording to claim 24, wherein there are at least three waxes in theplurality of waxes which have melting points in the range of 86° C. to90° C., and 91° C. to 94° C., and 90° C. to 97° C., and 104° C. to 116°C.
 30. The phase change composition according to claim 24, wherein thereare four waxes in the plurality of waxes and the melt points of thewaxes are in the ranges of 86° C. to 90° C., and 91° C. to 94° C., and90° C. to 97° C., and 104° C. to 116° C.
 31. A phase change compositionthat is a solid at ambient temperature and a liquid at an elevatedtemperature above ambient temperature, adapted for use in selectivedeposition modeling to form a three-dimensional object, comprising asemi-crystalline mixture of components including a tetra-amide, amono-amide wax and at least one ester component for hydrogen-bondingwith the tetra-amide and the mono-amide wax.
 32. The phase changecomposition according to claim 31, wherein the at least one estercomponent is selected from the group consisting of ester tackifiers andester plasticizers.
 33. The phase change composition according to claim32, wherein the ester tackifier is a modified rosin ester.
 34. The phasechange composition according to claim 33, wherein the modified rosinester is a glycerol tri-ester of hydrogenaced abietic acid.
 35. Thephase change composition according to claim 31, wherein the esterplasticizer is an alkyl benzene phthalate.
 36. The phase changecomposition according to claim 35, wherein the ester component comprisesan ester tackifier and an ester plasticizer.
 37. The phase changecomposition according to claim 36, wherein the ester tackifier is amodified rosin ester and the ester plasticizer is an alkyl benzenephthalate.
 38. The phase change composition according to claim 37,wherein the modified rosin ester is a glycerol tri-ester of hydrogenatedabietic acid.
 39. The phase change composition according to claim 31,wherein the ratio of the combined weight percentages of the tetra-amideand the mono-amide wax to the weight percentage of the ester componentin the composition ranges from about 0.75:1 to about 2.5:1.
 40. Thephase change composition according to claim 31, wherein the ratio of thecombined weight percentages of the tetra-amide and the mono-amide wax tothe weight percentage of the ester tackifier in the composition rangesfrom about 1:1 to about 3:1.
 41. The phase change composition accordingto claim 31, wherein there are at least two waxes present which havemelting points in the range of 86° C. to 90° C., and 91° C. to 94° C.,and 90° C. to 94° C., and 104° C. to 116° C.
 42. The phase changecomposition according to claim 31, wherein there are at least threewaxes present which have melting points in the range of 86° C. to 90°C., and 91° C. to 94° C., and 90° C. to 97° C., and 104° C. to 116° C.43. The phase change composition according to claim 31, wherein thereare four waxes in the plurality of waxes and the melt points of thewaxes are in the ranges of 86° C. to 90° C., and 91° C. to 94° C., and90° C. to 97° C., and 104° C. to 116° C.
 44. A phase change compositionthat is a solid at ambient temperature and a liquid at an elevatedtemperature above ambient temperature, adapted for use in selectivedeposition modeling to form a three-dimensional object, comprising asemi-crystalline mixture of components including a tetra-amide, amono-amide wax, at least one wax selected from the group consisting ofpetroleum waxes and synthetic waxes.
 45. The phase change compositionaccording to claim 44, further comprising a plasticizer.
 46. The phasechange composition according to claim 44, wherein there are at least twowaxes present which have melting points in the range of 86° C. to 90°C., and 91° C. to 94° C. and 90° C. to 97° C., and 104° C. to 116° C.47. The phase change composition according to claim 44, wherein thereare at least three waxes present which have melting points in the rangeof 86° C. to 90° C., and 91° C. to 94° C., and 90° C. to 97° C., and104° C. to 116° C.
 48. The phase change composition according to claim44, wherein there are four waxes present and the melt points of thewaxes are in the ranges of 86° C. to 90° C., and 91° C. to 94° C., and90° C. to 97° C., and 104° C. to 116° C.
 49. The phase changecomposition according to any of claims 1, 8, 18, 24, 31, or 44, furthercomprising at least one antioxidant.
 50. The phase change compositionaccording to any of claims 1, 8, 18, 24, 31, or 44, further comprising acolorant.
 51. A phase change composition that is a solid at ambienttemperature and a liquid at an elevated temperature above ambienttemperature, adapted for use in selective deposition modeling to form athree-dimensional object, comprising a semi-crystalline mixture ofcomponents including a tetra-amide, a mono-amide wax, a petroleum wax, apolyethylene wax, an ethylene-propylene copolymer wax, a modified rosinester, a hydrocarbon based aromatic resin, an alkyl benzene phthalate,at least one antioxidant and at least one colorant.
 52. The phase changecomposition according to claim 51, wherein the tetra-amide is present inan amount of about 5% to about 30% by weight, the mono-amide wax ispresent in an amount of about 15% to about 40% by weight, the petroleumwax is present in an amount of about 5% to about 25% by weight, thepolyethylene wax is present in an amount of up to about 15% by weight,the ethylene-propylene copolymer wax is present in an amount of up toabout 10% by weight, the tri-ester is present in an amount of about 10%to about 40% by weight, the aromatic resin is present in an amount of upto about 15% by weight, the alkyl benzene phthalate is present in anamount of up to about 10% by weight, each antioxidant is present in anamount of less than about 1% by weight. and the colorant is present inan amount of no greater than about 2% by weight, all weight percentagesbeing based on the total weight of the composition.
 53. The phase changecomposition according to claim 51, wherein at least two waxes presenthave melting points in the range of 86° C. to 90° C., and 91° C. to 94°C., and 90° C. to 97° C., and 104° C. to 116° C.
 54. The phase changecomposition according to claim 51, wherein at least three waxes presenthave melting points in the range of 86° C. to 90° C., and 91° C. to 94°C. and 90° C. to 97° C., and 104° C. to 116° C.
 55. The phase changecomposition according to claim 51, wherein there are four waxes presentand the melt points of the waxes are in the ranges of 86° C. to 90° C.,and 91° C. to 94° C., and 90° C. to 97° C., and 104° C. to 116° C.